Antistatic polymeric materials containing ethylene oxide condensation products of phenolic derivatives



United States Patent ANTISTATIC POLYMERIC MATERIALS CONTAIN- ING ETHYLENE OXIDE CONDENSATION PROD- UCTS OF PHENOLIC DERIVATIVES Lucien Sellet, Saddle River, N.J., assignor to Nopco Chemical Company, Newark, N.J., a corporation of New Jersey No Drawing. Filed Aug. 29, 1966, Ser. No. 575,537

1 Claim. (Cl. 117-139.5)

ABSTRACT OF THE DISCLOSURE Natural and synthetic polymeric materials containing water-soluble low volatility ethylene oxide condensation products of phenolic derivatives have antistatic properties. A typical example is an acrylic fiber treated with an ethylene oxide condensation product of a-methylbenzylphenol.

This application is a continuation-in-part of my copending application Ser. No. 281,017, Sellet filed May 16, 1963, now abandoned.

This invention relates to new surface active materials, more particularly to a new class of surface active materials that impart improved processing properties to vegetable, animal and synthetic fibers such as antistatic properties, due to the unique properties of these surface active materials.

In the past, it has been necessary to apply various different compositions to fibers to effect various properties in the fibers. For example, in the case of processing continuous filaments of cellulose acetate and other cellulose material suitable for the production of fine spun yarns, the continuous filaments are usually treated with a suitable lubricating composition as they emerge from the spinning cabinet or metier in which they are formed so as to lubricate and condition the filament. Then a plu rality of said lubricated conditioned filaments are associated together in the form of a bundle or tow. While the continuous filaments are associated together in the form of a bundle or tow, a separate lubricant containing a surface active agent is applied thereto in the desired amount to condition said filament and improve the subsequent processability of the filament. The lubricated and conditioned continuous filaments, thus obtained are then severed into staple fibers of the desired length, after which they may be spun into yarn. Other fibers such as those produced by spinning from a melt or by coagulation from aqueous or organic solvent solutions or dispersions require equivalent treatment and require compositions which may vary in the ratio and in the components depending upon the nature of the fiber and upon the requirements for lubricating, conditioning and antistatic control.

In the past it has been necessary to apply separate agents or treatments to the filaments or fibers to impart difierent improved processing characteristics to the fibers or filaments. For example a lubricating composition is applied to the yarn to impart a suitable degree of flexibility as well as desirable frictional qualities so that the yarn contained in continuous filaments may be processed satisfactorily into fine spun yarn. Separate conditioning agents or treatments are also applied to said filaments to render the filaments antistatic so as to avoid the generating of excessive static electricity which would render processing exceedingly difficult if not impossible. Also other conditioning agents are continually applied to said filaments to lower the draw force of the fibers so as to allow the fibers to be processed into yarns. This is necessary since, if the draw force of the filaments or fibers were not lowered, processing of the fiber or filaments would become exceedingly difiicult, if not impossible. Other separate agents or separate treatments may be applied to the fiber to modify other processing characteristics of the fiber.

The separate applications of different lubricants is not only uneconomical but also inconvenient. The development of a satisfactory single composition, which could be applied in the form of a water emulsion or hydrocarbon solution, for example, to continuous filament or fibrous materials, such as cellulose acetate, nylon, and the like as they emerge from the spinning cabinet or metier where the fibers are formed or before the processing of the fibers has begun and which would impart to fibers, most of the desired treating or processing properties such as static resistance, reduction of the draw force, lubricating and conditioning characteristics, has long been desired in the art.

In the past many of the processing agents utilized to impart improved processing characteristics to fibers or filaments have been found to have exceedingly short shelflife. In many cases this has caused the antistatic proper ties and the lubricating and conditioning properties of the treated fiber to be destroyed, a few days after application of the treating agent. Hence, it has been necessary to reapply the treating agent to the fibers every few days. This has proven both time-consuming and costly due to the fact that it has been necessary to apply these treating fibers or the filaments due to the loss of these agents from the fiber or filaments to the atmosphere.

It is an object of this invention to provide a method of both lubricating and conditioning various fibers as well as imparting other improved processing properties to fiber or fibrous materials such as antistatic properties, and the reduction of the fiber to fiber and fiber to metal friction. It is a further object of this invention to provide a method whereby fibrous materials may be treated for processing by the application of one treating agent. Another object of this invention is to provide a treating agent that has good shelf-aging properties. Still another object is to provide improved natural and synthetic polymeric materials which have been treated with the treating agents of this invention. Other objects of the invention will be obvious and will in part appear hereinafter.

I have unexpectedly discovered that both natural and synthetic polymeric materials such as textiles, fibers or filaments, sheets and the like treated with from about 0.01% to about 1.3% by weight, preferably from about 0.25% to about 0.7%, based on the weight of the dry material of a surface active treating agent consisting essentially of the water soluble condensation products of particular aromatic compounds containing an aromatic moiety and having at least one phenolic hydroxy group with from about 9 to 19 moles of ethylene oxide per phenolic hydroxy group contained within said compound, have improved processing properties so that such materials can be easily processed into yarn, sheets and the like. The improved processing properties of these materials are due to the fact that the above condensation products impart upon application to materials suitable degrees of flexibility, antistatic properties, desirable metal to fiber and fiber to fiber frictional qualities as well as other desirable processing properties which allow these synthetic or natural materials to be easily processed to form yarn, sheets and the like. Another advantage in utilizing these condensation products as treating agents is that they are soluble in water as well as hydrocarbon solvents which allows them to be easily applied to the natural or synthetic polymeric materials to be treated. Since these compounds impart to the polymeric materials to be treated all of the necessary properties to easily process such materials into yarns, sheets and the like there is no necessity for applying different treating agents at each processing stage to the polymeric materials to effect processing of these polymeric materials. Furthermore, the improved processing properties which these compounds impart to the natural or synthetic polymeric materials are not lost by the polymeric materials by aging or storage. Hence, these compounds may be applied to the fibers a short time before any stage of the processing has begun Without the danger that the processing properties of the fibers, filaments, sheets or the like will be destroyed.

I have additionally found that the aforementioned condensation products impart antistatic properties to resin films and sheets such as polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, and the like.

The textile lubricating agents which impart the improved processing properties to the fibers in accordance with this invention are formed by condensing particular compounds containing an aromatic moiety and having at least one phenolic hydroxy group with from about 9 to about 19 moles, preferably 9 to moles, per phenolic hydroxy group of ethylene oxide. The condensation of ethylene oxide with a phenolic compound is well known in the art and any conventional method of condensing ethylene oxide with a phenolic compound may be utilized to prepare the treating agent which can be utilized for treating textiles in accordance with this invention.

Generally, in order to prepare the textile treating agent for use in accordance with this invention, the aromatic compound containing at least one phenolic hydroxy group should be condensed with from about 9 to about 19 moles of ethylene oxide per phenolic hydroxy group contained within said compound. If less than 9 moles of ethylene oxide per phenolic hydroxy group are utilized the water solubility of the resulting compound is reduced so that the compound cannot be easily applied to the fibers to be treated. If more than about 19 moles of ethylene oxide per reactive hydroxy group contained within said compound is utilized, the textile treating properties of the resulting product are reduced to such an extent that the product is not useful as a textile treating agent.

The aromatic compound containing one phenolic group which are condensed with ethylene oxide to produce the treating compounds which are utilized in accordance with this invention and have the aforementioned beneficial textile treating properties are preferably selected from the group consisting of the following compounds:

SO -R wherein R is an aryl or substituted aryl radical containing from about 6 to 24 carbon atoms, such as phenyl, chlorophenyl, octyl phenyl, diphenyl, hydroxy benzyl,

dioctyl-o-hydroxy benzyl, 2, hydroxy-3-(ortho hydroxy benzyl) phenyl and the like and X is selected from the group consisting of hydrogen, chlorine, bromine, and straight and branched chain alkyl radicals containing from about 1 to about 15 carbon atoms such as nonyl, methyl, ethyl, octyl, tert. octyl propyl, isopropyl, dodecyl, pentadecyl and the like, and

Rt 5-K 1'1 X wherein R is an aryl or substituted aryl radical containing from about 6 to about 24 carbon atoms such as phenyl, chlorophenyl, octyl phenyl, diphenyl, hydroxy benzyl, di-octyl-o-hydroxy benzyl, 2,hydroxy-3-(ortho hydroxy benzyl) phenyl, and the like and X is selected from the group consisting of hydrogen, chlorine, bromine, and straight and branched chain alkyl radicals containing from about 1 to about 15 carbon atoms such as nonyl, methyl, ethyl, octyl, tert. octyl, propyl, isopropyl, dodecyl, pentadecyl and the like and R is selected from the group consisting of hydrogen and alkyl radicals having from about 1 to 5 carbon atoms such as methyl, ethyl, propyl, butyl, amyl and the like and R is an alkyl radical having from about 1 to 5 carbon atoms such as methyl, ethyl, propyl, amyl and the like.

The novel textile treating agents of this invention can be applied directly to the natural or synthetic fibers by any conventional means such as by means of a spray, by means of a bath, by means of an aqueous solution or by dissolving the treating agents in an organic solvent such as ether, methyl alcohol, ethyl alcohol, acetone, etc. The treating agents of this invention are particularly advantageous in that they may easily be applied to the filaments or fibers at the spinning cabinet where said filaments or fibers are formed or at the conclusion of the spinning operation. These treating agents may be applied to the natural fibers at the picking stage since they are soluble or dispersible in water and hydrocarbon solvents. Generally, the treating agents are applied before any processing is carried out by means of spray with a minimum of water or dissolved or dispersed in an organic solvent such as ether to avoid fiber wetting. After the treating agent is applied to the fiber, the fiber is ready for further processing, i.e., the carding, roving, spinning, and weaving steps. It is during these steps that the novel textile treating agents impart improved softening to the fibers, prevent card loading and lickering loading during processing and impart very satisfactory spinning characteristics thereto, particularly when treated cellulose acetate or other organic derivatives of cellulose acetate are spun. These treating agents provide antistatic, noncorrosive properties and control of the fiber to fiber and the metal to fiber coefficient of friction in the treated fibers.

The treating agents of this invention are generally applied to textile material in amounts of from about 0.01% to about 1.3% of the solid treating agent, by weight of the textile material to be treated. Generally for best results, it is preferred to utilize 0.25% to about 0.7% of the solid treating agent of this invention by weight of the fiber to be treated, of the treating agent. Utilizing amounts of treating agents below 0.01% by weight of the fiber, does not sufficiently affect the treating properties of the fibers to be commercially feasible, Amounts of the treating agent above 1.3% by Weight of the fiber may be utilized. However, such large amounts of treating agent are seldom utilized due to the fact that these large amounts create a tacky affect on the textile material, making them difficult to process during the steps of carding, roving, spinning, etc.

Textile' materials which may be treated in accordance with this invention include cellulose acetate, nylons such as Nylon 66, Dacron (polyethylene terephthalate), acrylic fibers such as Orlon and Acrilan (polyacrylonitrile polymer), viscose rayon, polyvinylidene chloride, copolymers of acrylonitrile and polyvinyl alcohol, polyethylene, polypropylene, cotton, wool, linen, silk, casein, vicara, and the like.

By the term textile material as used throughout the specification and claims I mean natural and synthetic textile material whether in the form of fiber, continuous or spun yarns, filaments, rovings, slivers,or tops. By the term natural or synthetic polymer materials I mean textile materials as well as resin sheets, films, shapes and the like derived from polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyethylene terephthalate and the like.

For a fuller understanding of the nature and objects of theinvention, reference may be had to the following examples which are given merely as further illustrations of the invention and are not to be construed in a limiting sense.

Example I A. Preparation of a-methyl benzyl para phenl.-95 lbs. of molten phenol (-1 mole) and a catalyst consisting of 1.47 lbs. of boron trifluoride and 0.15 lb. of an aqueous solution consisting of 50% by weight of hypophorphorous acid were added to a reaction vessel. The reaction vessel was heated until it reached a temperature of about 70 C. At this temperature 52.5 lbs. of styrene were slowly introduced into the vessel while maintaining the temperature of the vessel at about 70 C. After all of the styrene had been added, the temperature of the vessel was maintained for one hour at about 70 C. During this period, an exothermic reaction was produced which indicated that the styrene had reacted with the molten phenol forming a greyish brown liquid. After this period the liquid was neutralized to a pH of about 8.0 by the addition of 4.6 lbs. of a solution containing 25% by weight of sodium methylate dissolved in 75% by weight of methyl alcohol while maintaining the temperature at about 70 C. After all of the sodium methylate solution had been added to the reaction vessel, 0.75 lb. of diatomaceous earth as a filter aid were added under constant stirring while maintaining the temperature at 70 C. The liquid within the reaction vessel was filtered through a filter press. The clear liquid filtrate thus obtained which contained the reaction product of styrene and phenol was then charged into a kettle fordistilling the excess phenol and excess methanol from the product. The excess phenol was removed from the product by distilling the filtrate at a temperature of about 175 C. under a vacuum of about 55 millimeters of mercury. About 48 lbs. of phenol were collected during the stripping. The remaining traces of phenol were sparged with nitrogen. The remaining liquid product was subsequently cooled to room temperature under nitrogen atmosphere to maintain the clear color of the liquid product. The resulting product was a clear, yellow to light amber liquid. A small portion of the cooled liquid was removed and tested for its refractive index. The refractive index was 1.5880:t0.-0020 which indicated that the product was a-methyl benzyl para phenol.

B. Preparation of the condensation product of one mole of a-methyl benzyl para phenol with about 9.0 moles of ethylene oxide.230 lbs. of the product of Part A and 2.3 lbs. of potassium hydroxide were charged into a reaction kettle. The reaction kettle was heated to a temperature of about 190 C. At this temperature 460 lbs. of ethylene oxide were introduced into the reaction vessel. After all of the ethylene oxide was introduced into the reaction vessel, the reaction vessel was maintained at a temperature of about 190 C. for a period of about 7 hours. At the end of this period, the reaction product was cooled to room temperature. 5 grams of this cooled reaction product were then dissolved in grams of water. The cloud point of this solution was about 60 C. which indicated that approximately nine moles of ethylene oxide had condensed with about 1 mole of a-methyl benzyl para phenol. The pH of this solution was 7.0105.

Example II This example is directed to producing the condensation product of 1 mole of a-methyl benzyl ortho phenol with about 9.0 moles of ethylene oxide.

230 lbs. of a-methyl benzyl ortho phenol containing about pure ortho isomer and 2.3 lbs. of potassium hydroxide were charged into a reaction kettle. The reaction kettle was heated to a temperature of about C. At this temperature, 500 lbs. of ethylene oxide were in troduced into the reaction vessel. After all of the ethylene oxide was introduced into the reaction vessel, the reaction vessel was maintained at a temperature of about 190 C. for a period of about 7 hours. At the end of this period, the reaction product was cooled to room temperature. 5 grams of the reaction product were then dissolved in 100 grams of water. The cloud point of this solution was about 60 C. which indicated that about nine moles of ethylene oxide had condensed with one mole of a methyl benzyl ortho phenol. The pH of this solution was 7.0:05.

Example III This example is directed to producing the condensation product of 1 mole of a-methyl benzyl para phenol with 15 moles of ethylene oxide.

233 lbs. of solid a-methyl benzyl para phenol which were prepared in Part A of Example I and 0.2 lb. of potassium hydroxide were charged into a reaction kettle. The reaction kettle was heated to a temperature of about 190 C. At this temperature 767 lbs. of ethylene oxide were introduced into the reaction vessel. After all of the ethylene oxide was introduced into the reaction vessel the reaction vessel was maintained at a temperature of about 190 C. for a period of about 7 hours. After this period the reaction product was cooled to room temperature. 5 grams of the reaction product were then dissolved in 95 grams of water. The cloud point of this solution was about 84 C. which indicated that about '15 moles of ethylene oxide had condensed with one mole of a-methyl benzyl para phenol. The pH of this solution was 70:05.

Example IV This example is directed to producing the condensation product of 1 mole of 4-methyl-4-hydroxy diphenyl sulfone and 19 moles of ethylene oxide.

248 lbs. of 4-methyl-4'-hydroxy diphenyl sulfone and 0.3 lbs. of flaked potassium hydroxide were introduced into a reaction kettle. The reaction kettle was heated to a temperature of about 190 C. At this temperature 854 lbs. of ethylene oxide were introduced into the reaction vessel over a period of about 6 hours. During the addition the temperature of the reaction vessel was maintained at about 190 C. At the end of this period the reaction product was cooled to room temperature. 5 grams of this reaction product were then dissolved in 95 grams of water. The cloud point of this product was about 54 C. which indicated that about 19' moles of ethylene oxide condensed with one mole of 4-methyl-4-hydroxy diphenyl sulfone.

Example V This example is directed to testing products produced by Examples I, II, III and IV on cellulose acetate, nylon and Dacron for their antistatic properties.

Each of the products prepared according to Examples I, II, III and IV were applied individually to separate yarns of cellulose acetate, Nylon 66 and Dacron by first dissolving each of the products produced by Examples I, II, III and IV separately in a s-ufiicient amount of ether to sufiiciently wet the yarns and then applying the ether solution to the particular yarn. The ether was evaporated from the yarn so than an 0.8% by weight of each product (based on the weight of the yarn which is to be treated) remained on the yarns. One piece of Nylon 66, Dacron and cellulose acetate yarn was not treated with any of the test solutions and there samples were designated as Blanks.

The yarns (both treated and Blanks) were tested for antistatic properties after conditioning for 24 hours at 50% relative humidity and 72 F. by the aforementioned procedure. First, a potential of 180 volts was applied to the individual yarns by connecting the yarns to the positive and negative terminal of a battery. The contact was then broken and the yarns were directly attached to a voltmeter which indicated the voltage of each individual yarn. After breaking the contact, if a good antistatic agent was present on the yarn, the charge would quickly leak off. This was shown by the needle of the voltmeter dropping rapidly from 180 volts to volts. The readings which are recorded in the following table are the time in seconds for the voltmeter needle to fall from 160 volts to 80 volts (half life of the fiber). The designation which appears in the following table indicates that no reading was taken.

TABLE I Half-life (seconds) Yarns treated with the following products Nylon 66 Cellulose Dacron acetate a-Methyl benzyl para phenol plus 9 moles of ethylene oxide (Example I). 15;l;4 a-Methyl benzyl ortho phenol plus 9 moles of ethylene oxide (Example II 423:6 440:!16 50;l:6 a-Methyl benzyl para phenol plus 15 moles of ethylene oxide (Example II 350;};57 4-methyl-4-hydroxy diphenyl sulfone plus 19 moles of ethylene oxide (Example IV) 13;12 760:1;50 19:1;4

lank 200,000 200,000 200,000

As can be seen from the above table, the compounds of this invention markedly increase the antistatic properties of nylon, Dacron and acetate by decreasing the capacity of these fibrous materials to hold electric charge. This is shown by the marked decrease of the half-life of the yarns treated by the compounds of this invention as compared to untreated yarns.

Example VI This example is directed to testing various yarns tested with the compounds of Examples II, III and IV for the fiber to fiber and fiber to metal friction.

The nylon, Dacron and acetate yarn samples prepared in Example V containing the test solutions of Examples II, III and IV and the blank were tested for their fiber to fiber and fiber to metal friction. The fiber to metal friction for each individual yarn treated with products of Examples II, III, and IV was determined by means of calculating the coefficient of friction for each individual yarn. The coefficient of friction was determined by means of the apparatus and method disclosed in U.S. Patent No. 2,285,255, Davis, June 2, 1942. This instrument measures the required time for a metal rider to travel a measured distance between two fixed points, on an inclined plane over the yarn to be tested. By varying the angle of the inclined plane until the time of travel of the rider was 75 seconds for a distance of 18 inches, the coefficient of friction was determined. The formula by which the coefficient of friction was calculated from the angle at which the metal rider traveled a distance of 18 inches in 75 seconds was as follows:

where U=the coefficient of friction; =angle of inclination to the horizontal; g=acceleration due to gravity; d=the distance of travel; T=the time of travel for distance d. The readings which are recorded in column 2 of the following table are the coefficients of friction. The designation which appears in Table II indicates that no reading was taken.

As can be seen by the above table, the compounds of this invention decrease the fiber to metal friction as seen by the marked decrease of the coefficient of friction of yarn as compared to untreated yarn.

The fiber to fiber friction for each individual yarn was determined by calculating the coeflicient of fiber to fiber friction for each individual yarn. The coefficient of fiber to fiber friction was determined in the same manner and utilizing the same means as that used in calculating the fiber to metal friction except that in place of the metal rider there was utilized a rider consisting of the fiber that is to be tested. The readings which are recorded in Table III are the coefficient of fiber to fiber friction.

As seen from the above table the compounds of this invention markedly decrease the fiber to fiber friction as seen by the decrease of the coefficient of fiber to fiber friction of the yarns treated with compounds of this invention as compared to untreated yarns. Hence as seen from Table II and III the compounds of this invention are excellent lubricating agents for textile materials since they decrease both the fiber to fiber and metal to fiber friction.

Example VII This example is directed to determining the volatility of the various compounds of this invention.

The volatility of each of the products prepared according to Examples II, III and IV were tested by placing one gram of each of the products of Examples II, III and IV in separate circular aluminum dishes. The aluminum dish had a diameter of 2% inches and a height of A3 inch. The aluminum dishes were placed in an air oven at 200 C. for a period of one hour. At the end of this period, the aluminum dish was placed in a calcium chloride desiccator where it was allowed to cool down to room temperatnre. After cooling to room temperature each sample was removed from the desiccator and weighed. The percent Percent volatility Weight of sample at 20 C. before placing in oven-Weight of sample at 20 C. after placing in oven Weight of sample at 20 C. after placing in oven The results of the test appear in Table IV.

TABLE IV Test samples: Percent volatility a-Methyl benzyl ortho phenol+9 moles of ethylene oxide (Example II) 8.3 a-Methyl 'benzyl para phenol-[- moles of ethylene oxide (Example III) 4.6 4-methyl-4-hydroxy dip'henyl sulfone+l9 moles of ethylene oxide (Example IV) 3.7

As seen from the above table the compounds of this invention are not volatile and do not evaporate easily into the air even at high temperatures. This property makes them suitable as textile treating agents since they do not volatilize but remain on the fiber giving enhanced treating properties to the fiber to which they are applied.

Example VIII This example is directed to determining the shelf life of antistatic agents such as the condensation product of one mole of a-methyl benzyl para phenol with about 9 moles of ethylene oxide and the condensation product of one mole of u-methyl benzyl ortho phenol with 9 moles of ethylene oxide when applied to staple fibers of Nylon 66, Dacron and Acrilan.

The solid condensation product of one mole of oc-methyl benzyl para phenol condensed with about 9 moles of ethylene oxide (prepared in Example I) and the solid condensation product of one mole of a-methyl benzyl ortho phenol condensed with about 9 moles of ethylene oxide (prepared in Example II) were applied individually to separate staple fibers of Acrilan, nylon and Dacron. This was accomplished by first preparing separate solutions of the products of Examples I and II by dissolving each of these products separately in a sufiicient amount of ether to sufficiently wet the yarns. The solutions were applied to the particular fiber to be tested. The ether was evaporated from the fibers so that an 0.4% by weight of the products of Examples I and II (based on the weight of the yarn which is to be treated) remained on the fiber. The treated fibers were dried in a 125 F. oven for about one hour. After drying the treated fibers were conditioned by placing them for one hour in an atmosphere maintained at 55% relative humidity and 75 F.

The shelf life of the treated fibers or the eifective time of the antistatic agent on the fibers was determined as follows. The conditioned fibers were run on a carding machine through the bent wire teeth of the machine to disentangle the fibers and to arrange the fibers in a parallel position. The static electrical charge of fibers was read in seconds by means of an Electrostatic Locator as the fibers come ofi the bent wire teeth. This reading was recorded as the initial reading. The fibers were then aged by placing them in a 140 F. oven for 7 days during which time the static electrical charge built up on the fibers. After this period, the fibers were again run through the carding machine and the static electric charge was again recorded by means of the Electrostat Locator. The aging, carding and recording steps were repeated until the static electric charge on the fibers reached about 25,600 volts. It is at this charge that the fibers become unworkable so that it is impossible to card the fibers. No static electric charge readings of nylon, Dacron, or Acrilan fibers which were not treated with the above antistatic agents were taken 1 0 since these untreated fibers clung to the wire teeth of the carding apparatus and would not form parallel webs.

The results of the shelf aging tests appear in the following table.

TABLE V.SHELF AGING TESTS ON DACRON, NYLON AND ACRILAN SYNTHETIC FIBERS UTILIZING THE OF THIS INVENTION AS ANTISTATIC As seen from the above table the treating agents of this invention have a good shelf life when applied as antistatic agents to various fibers such as nylon, Acrilan and Dacron. This is emphasized by the fact that the fibers treated with the products of this invention retain their antistatic characteristics despite prolonged periods of aging.

The draw force of the various treated fibers was measured by means of a West Point Cohesion Tester disclosed in US. Patent No. 2,705,423. The draw force is a measure of the force in grams required to drag one fiber past another so that the fiber can be processed into yarn. The results of the test are recorded in Table VI. No draw force measurement was made of Nylon 66, Dacron or Acrilan fibers. which were not treated with the antistatic or lubricating agents of this invention since it was impossible to draw these fibers into yarn by utilizing the West Point Cohesion Tester disclosed in US. Patent No. 2,705,423.

TABLE VI.-DRAW FORCE TESTS ON SYNTHETIC FIBERS UTILIZING THE PRODUCTS OF THIS I TREATING AGENTS NVENTION AS As seen from the above table the products of this invention are excellent lubricants reducing the draw force of the synthetic fibers so as to allow them to be processed into yarns.

Example IX This example is directed to showing that the compounds of this invention are useful as internal antistatic agents for polyvinyl chloride films wherein the antistatic agent is incorporated in the film.

A resin mixture was prepared from the following formulation:

Component: Weight, grams Geon 103 (polyvinyl chloride) 150 Di-Z-ethyl hexyl phthalate 60 Paraplex G-62 (epoxidized soya bean oil) 7.5 Stearic acid 0.4 Metasap (a barium octoate-zinc octoate stabilizer) 3.0 Condensate of 1 mole of tit-methyl benzyl phenol with 9.0 moles of ethylene oxide (Example II) 3.0

The above formulation was mixed at room temperature and then milled at 335 F. for 5 minutes using a standard the exception that the ortho isomer of a-methyl benzyl phenol Was replaced with equimolar quantities of commercial nonylphenol and pentadecyl alcohol respectively.

The percent volatility of each of the above ethylene oxide condensation products was determined by placing five grams of each product in a separate aluminum dish. The aluminum dish had a diameter of 2% inch and a height of /a inch. The aluminum dish containing the sample was placed in an air oven at 200 C. for a period of one hour. At the end of this period, the aluminum dish was placed in a calcium chloride desiccator where it was allowed to cool to room temperature. After cooling to room temperature, the sample was removed from the desiccator and weighed. The percent volatility was determined by the following Thrope Rubber Mill where it was milled and sheeted to 15 formula:

Percent volatility Weight of sample at C. before placing in oven-Weight of sample at 20 C. after placing in oven Weight of sample at 20 C. after placing in oven sheets of 39 mils thickness. After this period the sheets were cooled to room temperature. The sheets were cooled to room temperature. The sheets were tested for static electricity by the manner indicated in Example V. The sheets showed a half-life of 16,000 seconds.

A control was made utilizing the same formulation except that no condensation product of one mole of tit-methyl benzyl phenol with 9.0 moles of ethylene oxide were used in the formulation. This formulation was sheeted and milled in the manner indicated above. The final product The sample was then placed in an air oven at 200 C. for an additional hour, cooled in a desiccator and weighed. The percent volatility was determined after the second hour of heating. The percent volatility was then determined in the same manner after the third, fourth and fifth hours of heating. Results of these determinations are shown in Table VII below. The lower the percent volatility of the condensation product, the greater would be the amount of the condensate remaining on or in a polymeric material treated with the product.

was then tested for its antistatic properties in the manner of Example V. The half-life of the resin sheet used as a control was 88,000 seconds. As shown by the above table the products of this invention are excellent antistatic agents for polyvinyl chloride resin films.

Likewise the compounds of this invention are useful as external antistatic agents for polyvinyl chloride films wherein they are applied as surface coatings to the film.

Example X This example is directed to demonstrating that the compounds used in this invention have lower volatilities than surface active materials such as the condensate of nonylphenol with 9 moles of ethylene oxide and the condensate of pentadecyl alcohol with 9 moles of ethylene oxide.

The products so tested were: (1) The condensation product of a mixture of ortho and para isomers of amethyl benzyl phenol with 9 moles of ethylene oxide was prepared by the alkoxylation procedure given in Example II above with the exception that a mixture of ortho and para isomers of a-methyl benzyl phenol was used instead of the ortho isomer of a-methyl benzyl phenol of Example II; (2) the condensation product of nonylphenol with 9 moles of ethylene oxide and (3) the condensation product of pentadecyl alcohol with 9 moles of ethylene oxide. The condensation products of (2) and (3) were prepared by the alkoxylation procedure given in Example II above with 0 The data in Table VII above show that only 5.6% by weight of the condensation product of a mixture of ortho and para isomers of a-methyl benzyl phenol+9 moles of ethylene oxide is lost by heating at 200 C. for 5 hours whereas 25% by weight of the condensation product of nonylphenol+9 moles of ethylene oxide and 93% by weight of the condensation product of pentadecyl alcohol +9 moles of ethylene oxide respectively are lost by heating at 200 C. for 5 hours. This difference in the volatility of the three condensation products was unexpected and surprising in that the condensation product based on amethyl benzyl phenol contained one less carbon atoms than either of the other condensation products.

What is claimed is:

Natural and synthetic polymeric materials having antistatic properties treated with from about 0.01% by weight to about 1.3% by weight of a water-soluble, low volatility product obtained by condensing (A) an aromatic hydroxy containing compound selected from the group consisting of:

13 14 and carbon atoms and R is an alkyl radical having from OH about 1 to 5 carbon atoms (B) with from about 9 to about 19 moles of ethylene oxide per hydroxy radical contained within said com- C-R 5 pound. References Cited X UNITED STATES PATENTS wherein R is selected from the group consisting of 22 533 555 2 260 613 ar'yl and substituted aryl radicals containing from 10 2525691 10/1950 Lee et a1 5 X about 6 to 24 carbon atoms, X is selected from the 2,790,764 4/1957 Lange et a1 117 139.5 X

group consisting of hydrogen, chlorine, bromine and alkyl radicals containing from about 5 to 15 carbon atoms, R is selected from the group consisting of hy- WILLIAM MARTIN Prlmary Examiner drogen and alkyl radicals having from about 1 to 5 15 T. G. DAVIS, Assistant Examiner. 

